Process for prevention and remediation of subterranean-formed metal-polymer complexes

ABSTRACT

A completion/stimulation/production fluid and injection mixture blend is disclosed. The blend may include an aqueous fluid, a polymer system and an injection mixture that includes a polyol, a natural sugar, an artificial sugar, or a combination thereof.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application which claims priorityfrom U.S. utility application Ser. No. 16/995,449, filed Aug. 17, 2020,which itself is a non-provisional application which claims priority fromU.S. provisional application No. 62/892,934, filed Aug. 28, 2019, eachof which is incorporated by reference herein in its entirety.

FIELD

Embodiments of the present disclosure generally relate to use of certaincomposition and methods for prevention and remediation ofsubterranean-formed metal-polymer formed complexes.

BACKGROUND

During hydraulic fracturing, perforations in the casing of a wellboreare formed at targeted zones of the subterranean formation prior to theintroduction of a fracturing fluid. The fracturing fluid is pumpedthrough a section of the wellbore. The hydraulic pressure from thefracturing fluid results in a network of fractures in the subterraneanformation. Further pumping of fracturing fluid causes the network offractures to continue to propagate through the subterranean formation.Proppant, typically sand, is then added to the fluid. The proppant issuspended within the fracturing fluid and is carried to the fractures inthe subterranean formation so as to keep the fractures open. Once thehydraulic pressure of the fracturing fluid is relieved, the fracturecollapses on the proppant within the fracture. The fractures then allowa pathway for the oil, gas and produced water to flow to the surface forrecovery and processing.

Typically, the formulation of fracturing fluid used depends on welltemperature and fluid design. Conventional fracturing fluids may includepolymer systems such as polyacrylamide slickwater, polyacrylamideslickwater-crosslinked, or traditional fracturing fluid polymer systems,for example, guar gum, guar gum + crosslinker, guar derivative, guarderivative crosslinked, carboxy methyl cellulose (CMC), or CMCcrosslinked. These polymer systems may crosslink with metals in thefracturing fluid such as zirconium, boron, titanium aluminum, iron,chromium, and hafnium. Unfortunately, the polymer systems may interactwith naturally occurring metals within the subterranean formulation inaddition to the metals present in the fracturing fluid. These naturallyoccurring metals may include, for example and without limitation,zirconium, boron, titanium aluminum, iron, chromium, hafnium, calcium,arsenic, antimony, molybdenum, strontium, zinc, iron, manganese, lead,barium, lithium and naturally occurring radioactive material (NORM).These interactions can cause persistent deposition resulting information damage in the subterranean formation, decreasing permeabilityand production of oil and gas from within the formation. This inventionoutlines new prevention and remediation methods for subterranean formedmetal-polymer complexes where the metal source is NOT intentionallyintroduced into the well at known levels, typically seen withcrosslinking agents of the fracturing fluids. This includes thefracturing water source as well as the native subterranean metal sourcesof unknown concentrations.

SUMMARY

The present disclosure provides for a completion/stimulation/productionfluid and injection mixture blend. The blend may include an aqueousfluid, a polymer system and an injection mixture that includes a polyol,a natural sugar, an artificial sugar, or a combination thereof.

BRIEF DESCRIPTION OF DRAWINGS

The present disclosure may be understood from the following detaileddescription when read with the accompanying figures. It is emphasizedthat, in accordance with the standard practice in the industry, variousfeatures may not be drawn to scale. In fact, the dimensions of thevarious features may be arbitrarily increased or reduced for clarity ofdiscussion.

FIG. 1 is a photograph of samples of a subterranean-formed metal polymercomplex and sorbitol solutions as described in Example 1.

FIG. 2 is a photograph of samples of a subterranean-formed metal polymercomplex and sorbitol solutions as described in Example 1.

FIG. 3 is a photograph of samples of a subterranean-formed metal polymercomplex and sorbitol solutions as described in Example 1.

FIG. 4 is a photograph of samples of a subterranean-formed metal polymercomplex and sorbitol solutions as described in Example 1.

FIG. 5 is a photograph of a series of samples of mixtures of an ironsolution and various compositions as described in Example 3.

DETAILED DESCRIPTION

A detailed description will now be provided. The following disclosureincludes specific embodiments, versions and examples, but the disclosureis not limited to these embodiments, versions or examples, which areincluded to enable a person having ordinary skill in the art to make anduse the disclosure when the information in this application is combinedwith available information and technology. In addition, the presentdisclosure may repeat reference numerals and/or letters in the variousexamples. This repetition is for the purpose of simplicity and clarityand does not in itself dictate a relationship between the variousembodiments and/or configurations discussed.

Various terms as used herein are shown below. To the extent a term usedin a claim is not defined below, it should be given the broadestdefinition persons in the pertinent art have given that term asreflected in printed publications and issued patents. Further, unlessotherwise specified, all compounds described herein may be substitutedor unsubstituted and the listing of compounds includes derivativesthereof.

Further, various ranges and/or numerical limitations may be expresslystated below. It should be recognized that unless stated otherwise, itis intended that endpoints are to be interchangeable. Where numericalranges or limitations are expressly stated, such express ranges orlimitations should be understood to include iterative ranges orlimitations of like magnitude falling within the expressly stated rangesor limitations (e.g., from about 1 to about 10 includes, 2, 3, 4, etc.;greater than 0.10 includes 0.11, 0.12, 0.13, etc.).

In certain embodiments of the present disclosure, an injection mixtureincluding a polyol, a natural and/or artificial simple sugar, a metalsalt of a polyol or natural and/or artificial sugars, or a combinationthereof is blended with a completion/stimulation/production fluid toremediate and/or retard subterranean-formed metal-polymer complexes insubterranean formations in such treatments as fracturing,post-fracturing treatments (such as remediation), including, but notlimited to remediation as shown in Example 1, production, orre-fracturing. In other embodiments, the polyol, a natural and/orartificial simple sugar, a metal salt of a polyol or natural and/orartificial sugars, or a combination thereof is mixed directly with thecompletion/stimulation/production fluid. As used herein, acompletion/stimulation/production fluid may be used in any or all ofsuch treatments.

The completion/stimulation/production fluid may include an aqueous fluidsuch as water and one or more polymer systems such as polyacrylamideslickwater, polyacrylamide slickwater-crosslinked, or traditionalfracturing fluid polymer systems, for example, guar gum, guar gum +crosslinker, guar derivative, guar derivative crosslinked, carboxymethyl cellulose (CMC), or CMC crosslinked. In certain embodiments ofthe present disclosure, the polymer system may include a polymer, suchas a copolymer containing at least two different monomeric units. Inother embodiments, the polymer is a homopolymer containing only one typeof monomeric unit.

In certain embodiments, the polymer includes component (A) as amonomeric unit. Component (A) is represented by the formula:

Within component (A), R₁ may be hydrogen, a C₁-C₆ alkyl, or a phenyl.Within component (A), R₂ may be a C₁-C₂₂ alkylene, a carboxylic C₁-C₂₂alkylene ester, benzyl, an alkyl benzyl containing C₁-C₁₆ carbon atoms,or a benzyl amide. Within component (A), X may be hydrogen, lithium,sodium, potassium, ammonium, or a mixture thereof.

Component (A) may be present in the polymer as a monomeric unit in anamount ranging from about 0.1 to 99.9 weight percent, or 0.5 to 99.5weight percent, or 1 to 99 weight percent, or 10 to 90 weight percent,or 20 to 80 weight percent, or 30 to 70 weight percent, or 40 to 60weight percent, or 45 to 55 weight percent based on a total weight ofthe polymer.

In certain embodiments, the polymer includes component (B) as amonomeric unit. Component (B) is represented by the formula:

Within component (B), R₁ may be hydrogen, a C₁-C₆ alkyl, or a phenyl.Within component (B), R₃ may be a C₁-C₂₂ alkylene, a C₁-C₂₂ alkyl amide,a phenyl amide, a benzyl amide, a carboxylic C₁-C₂₂ alkylene ester, aphenyl, a benzyl, or a benzyl alkyl containing C₁-C₁₆ carbon atoms.Within component (B), X may be hydrogen, lithium, sodium, potassium,ammonium, or a mixture thereof.

Component (B) may be present in the polymer as a monomeric unit in anamount ranging from about 0.1 to 99.9 weight percent, or 0.5 to 99.5weight percent, or 1 to 99 weight percent, or 10 to 90 weight percent,or 20 to 80 weight percent, or 30 to 70 weight percent, or 40 to 60weight percent, or 45 to 55 weight percent based on a total weight ofthe polymer.

In certain embodiments, the polymer includes component (C) as amonomeric unit. Component (C) is represented by the formula:

Within component (C), R₁ may be hydrogen, a C₁-C₆ alkyl, or a phenyl.Within component (C), R₄ may be a C₁-C₂₂ alkylene, a C₁-C₂₂ alkyl amide,a phenyl amide, a benzyl amide, a carboxylic C₁-C₂₂ alkylene ester, aphenyl, a benzyl, or a benzyl alkyl containing C₁-C₁₆ carbon atoms.Within component (C), X may be hydrogen, lithium, sodium, potassium,ammonium or a mixture thereof.

Component (C) may be present in the polymer as a monomeric unit in anamount ranging from about 0.1 to 99.9 weight percent, or 0.5 to 99.5weight percent, or 1 to 99 weight percent, or 10 to 90 weight percent,or 20 to 80 weight percent, or 30 to 70 weight percent, or 40 to 60weight percent, or 45 to 55 weight percent based on a total weight ofthe polymer.

In certain embodiments, the polymer includes component (D) as amonomeric unit. Component (D) is represented by the formula:

Within component (D), R₁ may be hydrogen, a C₁-C₆ alkyl, or a phenyl.Within component (D), R₅ may be a C₁-C₂₂ alkylene, a C₁-C₂₂ alkyl amide,a phenyl amide, a benzyl amide, a carboxylic C₁-C₂₂ alkylene ester, abenzyl, or a benzyl alkyl containing C₁-C₁₆ carbon atoms.

Component (D) may be present in the polymer as a monomeric unit in anamount ranging from about 0.1 to 99.9 weight percent, or 0.5 to 99.5weight percent, or 1 to 99 weight percent, or 10 to 90 weight percent,or 20 to 80 weight percent, or 30 to 70 weight percent, or 40 to 60weight percent, or 45 to 55 weight percent based on a total weight ofthe polymer.

In certain embodiments, the polymer includes component (E) as amonomeric unit. Component (E) is represented by the formula:

Within component (E), R₁ may be hydrogen, a C₁-C₆ alkyl, or a phenyl.Within component (E), R₆ may be hydrogen or an alkyl containing C₁-C₂₂carbon atoms. Within component (E), R₇ may be hydrogen or an alkylcontaining C₁-C₂₂ carbon atoms.

Component (E) may be present in the polymer as a monomeric unit in anamount ranging from about 0.1 to 99.9 weight percent, or 0.5 to 99.5weight percent, or 1 to 99 weight percent, or 10 to 90 weight percent,or 20 to 80 weight percent, or 30 to 70 weight percent, or 40 to 60weight percent, or 45 to 55 weight percent based on a total weight ofthe polymer.

In certain embodiments, the polymer includes component (F) as amonomeric unit. Component (F) is represented by the formula:

Within component (F), R₁ may be hydrogen, a C₁-C₆ alkyl, or a phenyl.Within component (F), R₈ may be a C₁-C₂₂ alkylene, a C₁-C₂₂ alkyl amide,a phenyl amide, a benzyl amide, a benzyl, or a benzyl alkyl containingC₁-C₁₆ carbon atoms. Within component (F), R₉ may be hydrogen or analkyl containing C₁-C₂₂ carbon atoms. Within component (F), R₁₀ may behydrogen or an alkyl containing C₁-C₂₂ carbon atoms.

Component (F) may be present in the polymer as a monomeric unit in anamount ranging from about 0.1 to 99.9 weight percent, or 0.5 to 99.5weight percent, or 1 to 99 weight percent, or 10 to 90 weight percent,or 20 to 80 weight percent, or 30 to 70 weight percent, or 40 to 60weight percent, or 45 to 55 weight percent based on a total weight ofthe polymer.

In certain embodiments, the polymer includes component (G) as amonomeric unit. Component (G) is represented by the formula:

Within component (G), R₁ may be hydrogen, a C₁-C₆ alkyl, or a phenyl.Within component (G), R₁₁ may be a carboxylic acid, a carboxylic salt, asulfonic acid, a sulfonic salt, a phosphonic acid salt, an alcohol, anamine, or a nitrile. When R₁₁ is a carboxylic salt, R₁₁ may be, forexample and without limitation, a lithium carboxylic salt, sodiumcarboxylic salt, potassium carboxylic salt, ammonium carboxylic salt, ora mixture thereof. When R₁ is a sulfonic salt, R₁ may be, for exampleand without limitation, a lithium sulfonic salt, sodium sulfonic salt,potassium sulfonic salt, ammonium sulfonic salt, or a mixture thereof.When R₁ is a phosphonic acid salt, R₁ may be, for example and withoutlimitation, a lithium phosphonic acid salt, sodium phosphonic acid salt,potassium phosphonic acid salt, ammonium phosphonic acid salt, or amixture thereof. When R₁ is an amine, R₁ may be, for example and withoutlimitation, a primary amine, secondary amine, or tertiary amine.

Component (G) may be present in the polymer as a monomeric unit in anamount ranging from about 0.1 to 99.9 weight percent, or 0.5 to 99.5weight percent, or 1 to 99 weight percent, or 10 to 90 weight percent,or 20 to 80 weight percent, or 30 to 70 weight percent, or 40 to 60weight percent, or 45 to 55 weight percent based on a total weight ofthe polymer.

In certain embodiments, the polymer includes component (H) as amonomeric unit. Component (H) is represented by the formula:

Within component (H), R₁ may be hydrogen, a C₁-C₆ alkyl, or a phenyl.Within component (H), R₁₂ may be a C₁-C₂₂ alkylene, a C₁-C₂₂ alkylamide, a phenyl amide, a phenyl, a phenyl alkylamino amide, or a phenylalkyl containing C₁-C₁₆ carbon atoms. Within component (H), R₁₃ may behydrogen, lithium, sodium, potassium, ammonium, or a mixture thereof.Within component (H), R₁₄ may be hydrogen, lithium, sodium, potassium,ammonium, or a mixture thereof.

Component (H) may be present in the polymer as a monomeric unit in anamount ranging from about 0.1 to 99.9 weight percent, or 0.5 to 99.5weight percent, or 1 to 99 weight percent, or 10 to 90 weight percent,or 20 to 80 weight percent, or 30 to 70 weight percent, or 40 to 60weight percent, or 45 to 55 weight percent based on a total weight ofthe polymer.

In certain embodiments, the polymer includes component (I) as amonomeric unit. Component (I) is represented by the formula:

Within component (I), R₉ is hydrogen or an alkyl containing C₁-C₂₂carbon atoms; R₁₀ is hydrogen or an alkyl containing C₁-C₂₂ carbonatoms; and Z is chlorine, bromine, iodine, or a mixture thereof.

Component (I) may be present in the polymer as a monomeric unit in anamount ranging from about 0.1 to 99.9 weight percent, or 0.5 to 99.5weight percent, or 1 to 99 weight percent, or 10 to 90 weight percent,or 20 to 80 weight percent, or 30 to 70 weight percent, or 40 to 60weight percent, or 45 to 55 weight percent based on a total weight ofthe polymer.

In certain embodiments, the polymer includes component (J) as amonomeric unit. Component (J) is represented by the formula:

Within component (J), R₁ is hydrogen, a C₁-C₆ alkyl, or a phenyl; R₂ isa C₁-C₂₂ alkylene, a C₁-C₂₂ alkyl amide, a phenyl amide, a phenyl, aphenyl alkylamino amide, or a phenyl alkyl containing C₁-C₁₆ carbonatoms; R₁₅ is hydrogen or an alkyl containing C₁-C₂₂ carbon atoms; R₁₆is hydrogen or an alkyl containing C₁-C₂₂ carbon atoms; and R₁₇ ishydrogen or an alkyl containing C₁-C₂₂ carbon atoms; Y is nitrogen,phosphorus, sulfur or a mixture thereof; and Z is chlorine, bromine,iodine or a mixture thereof.

Component (J) may be present in the polymer as a monomeric unit in anamount ranging from about 0.1 to 99.9 weight percent, or 0.5 to 99.5weight percent, or 1 to 99 weight percent, or 10 to 90 weight percent,or 20 to 80 weight percent, or 30 to 70 weight percent, or 40 to 60weight percent, or 45 to 55 weight percent based on a total weight ofthe polymer.

As monomeric units, the polymer may include any one of components(A)-(J) or any combinations thereof. In some embodiments, the polymeronly includes, as monomeric units, at least one of components (A)-(J) orany combinations thereof and does not include any monomeric units otherthan components (A)-(J). In certain embodiments, the polymer includeseach of components (A)-(J) as monomeric units. In some embodiments, thepolymer only includes each of components (A)-(J) as monomeric units anddoes not include any monomeric units other than components (A)-(J).

Examples of polyols, natural sugars, and artificial sugars for use inthe injection mixture include, but are not limited to:

a. Ethylene glycol, glycerol, erythritol, threitol, arabitol, xylitol,ribitol, sorbitol, galactitol, fucitol, inositols, volemitol, isomalt,maltitol, lactitol, maltotritol, maltoetraitol, polyglycitol, glucose,fructose, raffinose, and other related simple sugars;

b. Sugar Alcohols: Arabitol, Erythritol, Fucitol, Galactitol,Hydrogenated starch hydrolysates, Iditol, Isomalt, Lactitol, LycasinMaltitol, Mannitol, Mannosulfan, Ribitol, Sorbitol, Sorbitex, Threitol,Volemitol, Xylitol;

c. Monosaccharides: Fructose, Galactose, Glucose, Xylose, Dioses,Trioses, Tetroses, Pentoses, Hexoses, Heptoses, Octoses, Nonoses;

d. Disaccharides: Cellobiose, Isomaltose, Isomaltulose, Lactose,Lactulose, Maltose, Sucrose, Trehalose, Turanose;

e. Trisaccharides: Maltotriose Melezitose Raffinose;

f. Tetrasaccharides: Stachyose;

g. Other: Ascorbic acid, Glucuronic acid, Sulfoquinovose, Sialic acid,Glucosamine, Galactosamine, Lactic Acid, polylactic acid;

h. Cyclitol (Cyclic Polyols): Acarviosin, Aminocyclitol, Bornesitol,Ciceritol, Conduritol, Decahydroxycyclopentane, 3-Dehydroshikimic acid,5-Deoxyinositol, Dodecahydroxycyclohexane, Inositol, Ononitol(4-O-methyl-myo-inositol), Pinitol (3-O-methyl-chiro-inositol),Pinpollitol (di-O-methyl-(+)-chiro-inositol), Quebrachitol(2-O-methyl-chiro-inositol), Quinic acid, Shikimic acid, Validamycin,Valienol, Valienamine, Valienol, Viscumitol, Viscumitol(dimethyl-ether-muco-inositol), Ciceritol, a pinitol digalactoside,Phytic acid, Aminocyclitol;

i. Tetrols: Balsaminol A, Bromopyrogallol red, Citreorosein,Cortobenzolone, Landomycinone, Pentaerythritol, dipentaerythritol,Protopanaxatriol, Tetrahydroxy-1,4-benzoquinone,2,3,5,7-Tetrahydroxy-1,4-naphthalenedione, Tetrahydroxyanthraquinone.Tetrahydroxyanthraquinones, Pentoses (Apiose, Arabinose, Deoxyribose,L-Deoxyribose, Lyxose, Ribose, Ribulose, Xylose, Xylulose); and

j. Metal salts of a-h.

In certain embodiments, the polyol or the natural and/or artificialsimple sugar of a-h is encapsulated with a sparingly soluble material,such as with a resin, such as a paraffin or cottonseed oil coating. Insuch embodiments, the encapsulation is sparingly soluble and may inhibitsubterranean formed metal-polymer complexes upon slow dissolution. Inother embodiments, the polyol or natural and/or artificial simple sugaris not encapsulated. The polyol, natural and/or artificial simple sugarmay be present in the injection mixture in an amount of between 0.1% to99%, or between 0.1% and 20% by weight of the fluidcompletion/stimulation/production fluid and injection mixture blend. Theinjection mixture may also include (amounts based on total weight orvolume of the injection mixture): between 1 and 10,000 parts per million(ppm) of a corrosion inhibitor;

between 1 and 10,000 ppm of a biocide;

between 1 and 10,000 ppm of a clay stabilizer;

between 1-10 gallons per ton (gpt) friction reducer, or 1-60 parts perton (ppt) traditional fracturing fluids;

between 0.1-20 gpt metal crosslinker that is borate, zirconium,aluminum, chromium, titanium, based for crosslinking;

between 3 to 8 lb sand/gallon.

In certain embodiments, the injection mixture and/orcompletion/stimulation/production fluid and injection mixture blend doesnot include ethylenediaminetetraacetic acid (EDTA),propylenediaminetetraacetic acid (PDTA), nitrilotriacetic acid (NTA),N-(2-hydroxyethyl)ethylenediaminetriacetic acid (HEDTA),diethylenetriaminepentaacetic acid (DTPA), hydroxyethyliminodiaceticacid (HEIDA), cyclohexylenediaminetetraacetic acid (CDTA),diphenylaminosulfonic acid (DPAS),ethylenediiminodi(o-hydroxyphenylacetic) acid (EDDHA), glucoheptonicacid, gluconic acid, oxalic acid, malonic acid, succinic acid, glutaricacid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacicacid, phthalic acid, terephthalic acid, aconitic acid, carballylic acid,trimesic acid, isocitric acid, citric acid, acetic acid, erythorbicacid, formic acid, nitrilotriacetic acid (NTA), phosphonic acid, orsalts thereof. In other embodiments, a biocidal quaternary ammoniumpreservative is not included in the injection mixture and/orcompletion/stimulation/production fluid and injection mixture blend.

Without being bound by theory, it is believed that the polyols andnatural and/or artificial simple sugars interact, such as by binding orchelating, for example, with naturally occurring metals such aszirconium, boron, titanium aluminum, iron, chromium, and hafnium ineither the completion/stimulation/production fluid and/or thesubterranean heavy metal sources of unknown concentrations, such aszirconium, boron, titanium aluminum, iron, chromium, hafnium, calcium,arsenic, antimony, molybdenum, strontium, zinc, iron, manganese, lead,barium, lithium and naturally occurring radioactive material (NORM), orboth to form soluble and sparingly soluble metal complexes. In-situformation of soluble and sparingly soluble metal complexes downhole thatresult from this interaction may inhibit subterranean-formedmetal-polymer complex formation without encapsulation of the sugars orpolyols. The formation of soluble and sparingly soluble metal complexesmay retard specific formation damage and may reverse existing formationdamage when polymer residues remain in the formation, such as fromprevious formation treatments. Again, without being bound by theory, itis believed that the polyols and naturals and/or artificial sugarsretard iron deposition from naturally occurring iron present in theformation or in the completion/stimulation/production fluid. Thecomplexation reaction with naturally occurring metals may cause themetal-polymer complexes to disperse into solution or dissolve intosolution.

The completion/stimulation/production fluid and injection mixture blendmay be used in a number of processes, including, but not limited to,initial fracturing, during post-fracturing treatments, or duringre-fracturing of the same well. In initial fracturing, post-fracturing,and refracturing of the same well, the completion/stimulation/productionfluid and injection mixture blend is used as in initial fracturing,post-fracturing, and refracturing of the same well as if the injectionmixture was not present. In another embodiment, when seeking to inhibitthe formation of subterranean-formed metal-polymer complexes duringpost-production treatment, a remediation method includes injectinginjection mixture into a subterranean formation next to a well at apressure below the fracture pressure of the formation to remediatesubterranean-formed metal-polymer complexes present. A contact time (1minute to 100 days or one hour to seven days) is allowed and then themetal-polymer complex remediation mixture is pumped back to the surfaceafter the shut-in of the well.

Examples

The disclosure having been generally described, the following examplesshow particular embodiments of the disclosure. It is understood that theexample is given by way of illustration and is not intended to limit thespecification or the claims. All compositions percentages given in theexamples are by weight.

Example 1—In Example 1, a two gram sample of a subterranean-formed metalpolymer complex including metals of unknown concentrations were mixedwith a 2% solution and 4% solution (50 mL each) of sorbitol (SigmaAldrich) at 100° F. as shown in FIG. 1 . The pH ranged between 7.4 to8.4 prior to the complex's addition to the injection mixture. After 3hours, the solids began to swell noticeably as shown in FIG. 2 . After69 hours, the samples were even more swelled (approximately 80%) andwell dispersed as shown in FIG. 3 . As shown in FIG. 4 , after 5 days at100° F., both remediation mixtures dispersed nearly 100% of thesubterranean-formed metal polymer complex. The sorbitol solutionsremoved naturally occurring subterranean metals not intentionally addedfrom the polymer residue that remained in the subterranean formationafter fracturing. The more swelled and dispersed character of themetal-polymer complexes allows those complexes to be more easily removedand solubilized by the flow of the formation water to the surface. Anyremaining dispersed material may be removed at the surface separators.

Example 2—In Example 2, aqueous solutions of 10% citric acid, 70%sorbitol, 10% glucose, 10% EDTA Na5 and 4% pentaerythritol wereprepared. The 70% sorbitol solution was prepared using 60 grams ofdeionized water and 140 grams of sorbitol from Sigma Aldrich. Thesorbitol was added in small equal portions while using an overheadmixer. A small amount of heat was necessary to completely solubilize andprepare the stable final solution. The 10% glucose solution was preparedusing 20 grams of d(+)glucose from Sigma Aldrich and 180 ml of deionizedwater in a 250 mL beaker. The 4% pentaerythritol solution was preparedusing 192 grams of deionized water and pentaerythritol from SigmaAldrich. The solution produced was slightly hazy and required a smallamount of heat for clarity. The 40% EDTA Na5 from Dow Chemical wasdiluted. The solutions were combined with samples of asubterranean-formed metal polymer complex including metals of unknownconcentrations and then maintained at 150° F. for 24 hours. The resultsare show in Table 1.

TABLE 1 Subterranean- formed metal polymer complex, Remediation gramsSolution 24 Hour Observation Blank 1.87 g DI Water 100% undissolved, butis swelling, minor amount of discoloration to solution Sample 1 2.08 g10% EDTA 80-90% in Solution, Some Na5 Remains at the bottom glass Sample2 1.81 g 10% Citric Completely Solubilized Acid Sample 3 1.87 g 10%Sorbitol 70-80% in Solution, very swollen Sample 4 2.16 g 70% Sorbitol100% undissolved, Very little swelling - too high of concentrationSample 5 2.19 g 10% Glucose 100% undissolved, but is swelling, minoramount of discoloration to solution Sample 6 2.07 g 4% 100% undissolved,but is Pentaerythritol swelling, minor amount of discoloration tosolution

As shown in Example 2, the 10% sorbitol solution (sample 3) outperformedall other samples.

Example 3—In Example 3, for a known 50 ppm Iron (from FeCl₂tetrahydrate) in deionized water, 70% sorbitol was compared to 10%citric acid and 40% EDTA Na5 neutralized to pH 7 either with BAS-0186 orHCl. After centrifugation (2000 rpm, 5 min), as shown in FIG. 5 ,sorbitol 70% is comparable to 10% citric acid and 40% EDTA Na5 (basic)to control iron from precipitating.

-   -   CT1: Blank pH adjusted to 7;    -   CT2: 1 gpt 70% sorbitol, pH adjusted to 7;    -   CT3: Blank pH adjusted to 7;    -   CT4: 4 gpt 70% sorbitol, pH adjusted to 7;    -   CT5: 4 gpt 10% citric acid, pH adjusted to 7;    -   CT6: 4 gpt 40% EDTA Na5l, pH adjusted to 7 with HCl. CT6 showed        no solid after centrifugation if pH was unadjusted.

Depending on the context, all references herein to the “disclosure” mayin some cases refer to certain specific embodiments only. In other casesit may refer to subject matter recited in one or more, but notnecessarily all, of the claims. While the foregoing is directed toembodiments, versions and examples of the present disclosure, which areincluded to enable a person of ordinary skill in the art to make and usethe disclosures when the information in this patent is combined withavailable information and technology, the disclosures are not limited toonly these particular embodiments, versions and examples. Other andfurther embodiments, versions and examples of the disclosure may bedevised without departing from the basic scope thereof and the scopethereof is determined by the claims that follow.

What is claimed is:
 1. A completion/stimulation/production fluid andinjection mixture blend comprising: an aqueous fluid; a polymer system;and an injection mixture comprising a polyol, a natural sugar, anartificial sugar, or a combination thereof.
 2. Thecompletion/stimulation/production fluid and injection mixture blend ofclaim 1, wherein the polymer system is polyacrylamide slickwater,polyacrylamide slickwater-crosslinked, guar gum, guar gum andcrosslinker, guar derivative, guar derivative crosslinked, carboxymethyl cellulose (CMC), or CMC crosslinked.
 3. Thecompletion/stimulation/production fluid and injection mixture of claim1, wherein the polymer system includes: a polymer comprising monomericunits, wherein the monomeric units comprise: component (B) representedby the formula:

wherein within component (B), R₁ is hydrogen, a C₁-C₆ alkyl, or aphenyl; R₃ is a C₁-C₂₂ alkylene, a C₁-C₂₂ alkyl amide, a phenyl amide, abenzyl amide, a carboxylic C₁-C₂₂ alkylene ester, a phenyl, a benzyl, ora benzyl alkyl containing C₁-C₁₆ carbon atoms; and X is hydrogen,lithium, sodium, potassium, ammonium or a mixture thereof; or component(C) represented by the formula:

wherein within component (C), R₁ is hydrogen, a C₁-C₆ alkyl, or aphenyl; R₄ is a C₁-C₂₂ alkylene, a C₁-C₂₂ alkyl amide, a phenyl amide, abenzyl amide, a carboxylic C₁-C₂₂ alkylene ester, a phenyl, a benzyl, ora benzyl alkyl containing C₁-C₁₆ carbon atoms; and X is hydrogen,lithium, sodium, potassium, ammonium or a mixture thereof; or component(D) represented by the formula:

wherein within component (D), R₁ is hydrogen, a C₁-C₆ alkyl, or aphenyl; and R₅ is a C₁-C₂₂ alkylene, a C₁-C₂₂ alkyl amide, a phenylamide, a benzyl amide, a carboxylic C₁-C₂₂ alkylene ester, a benzyl, ora benzyl alkyl containing C₁-C₁₆ carbon atoms; or component (E)represented by the formula:

wherein within component (E), R₁ is hydrogen, a C₁-C₆ alkyl, or aphenyl; R₆ is hydrogen or an alkyl containing C₁-C₂₂ carbon atoms; andR₇ is hydrogen or an alkyl containing C₁-C₂₂ carbon atoms; or component(F) represented by the formula:

wherein within component (F), R₁ is hydrogen, a C₁-C₆ alkyl, or aphenyl; R₈ is a C₁-C₂₂ alkylene, a C₁-C₂₂ alkyl amide, a phenyl amide, abenzyl amide, a benzyl, or a benzyl alkyl containing C₁-C₁₆ carbonatoms; R₉ is hydrogen or an alkyl containing C₁-C₂₂ carbon atoms; andR₁₀ is hydrogen or an alkyl containing C₁-C₂₂ carbon atoms; or component(G) represented by the formula:

wherein within component (G), R₁ is hydrogen, a C₁-C₆ alkyl, or aphenyl; and R₁₁ is a carboxylic acid, a carboxylic salt, a sulfonicacid, a sulfonic salt, a phosphonic acid salt, an alcohol, an amine, ora nitrile; or component (H) represented by the formula:

wherein within component (H), R₁ is hydrogen, a C₁-C₆ alkyl, or aphenyl; R₁₂ is a C₁-C₂₂ alkylene, a C₁-C₂₂ alkyl amide, a phenyl amide,a phenyl, a phenyl alkylamino amide, or a phenyl alkyl containing C₁-C₁₆carbon atoms; R₁₃ is hydrogen, lithium, sodium, potassium, ammonium, ora mixture thereof; and R₁₄ is hydrogen, lithium, sodium, potassium,ammonium, or a mixture thereof; or component (I) represented by theformula:

wherein within component (I), R₉ is hydrogen or an alkyl containingC₁-C₂₂ carbon atoms; R₁₀ is hydrogen or an alkyl containing C₁-C₂₂carbon atoms; and Z is chlorine, bromine, iodine or a mixture thereof;or component (J) represented by the formula:

wherein within component (J), R₁ is hydrogen, a C₁-C₆ alkyl, or aphenyl; R₂ is a C₁-C₂₂ alkylene, a C₁-C₂₂ alkyl amide, a phenyl amide, aphenyl, a phenyl alkylamino amide, or a phenyl alkyl containing C₁-C₁₆carbon atoms; R₁₅ is hydrogen or an alkyl containing C₁-C₂₂ carbonatoms; R₁₆ is hydrogen or an alkyl containing C₁-C₂₂ carbon atoms; andR₁₇ is hydrogen or an alkyl containing C₁-C₂₂ carbon atoms; Y isnitrogen, phosphorus, sulfur or a mixture thereof; and Z is chlorine,bromine, iodine or a mixture thereof; or combinations thereof.
 4. Thecompletion/stimulation/production fluid and injection mixture blend ofclaim 1, wherein the polyol, natural sugar or artificial sugar isethylene glycol, glycerol, erythritol, threitol, arabitol, xylitol,ribitol, sorbitol, galactitol, fucitol, inositols, volemitol, isomalt,maltitol, lactitol, maltotritol, maltoetraitol, polyglycitol, glucose,fructose, raffinose, a combination thereof, or a metal salt thereof. 5.The completion/stimulation/production fluid and injection mixture blendof claim 1, wherein the polyol, natural sugar or artificial sugar isArabitol, Erythritol, Fucitol, Galactitol, Hydrogenated starchhydrolysates, Iditol, Isomalt, Lactitol, Lycasin Maltitol, Mannitol,Mannosulfan, Ribitol, Sorbitol, Sorbitex, Threitol, Volemitol, Xylitol,combinations thereof, or a metal salt thereof.
 6. Thecompletion/stimulation/production fluid and injection mixture blend ofclaim 1, wherein the polyol, natural sugar or artificial sugar isFructose, Galactose, Glucose, Xylose, Dioses, Trioses, Tetroses,Pentoses, Hexoses, Heptoses, Octoses, Nonoses, combinations thereof, ora metal salt thereof.
 7. The completion/stimulation/production fluid andinjection mixture blend of claim 1, wherein the polyol, natural sugar orartificial sugar is a disaccharide or a metal salt thereof.
 8. Thecompletion/stimulation/production fluid and injection mixture blend ofclaim 1, wherein the polyol, natural sugar or artificial sugar isAscorbic acid, Glucuronic acid, Sulfoquinovose, Sialic acid,Glucosamine, Galactosamine, Lactic Acid, polylactic acid, combinationsthereof, or a metal salt thereof.
 9. Thecompletion/stimulation/production fluid and injection mixture blend ofclaim 1, wherein the polyol, natural sugar or artificial sugar iscyclitol or a metal salt thereof.
 10. Thecompletion/stimulation/production fluid and injection mixture blend ofclaim 1, wherein the polyol, natural sugar or artificial sugar istetrol.
 11. The completion/stimulation/production fluid and injectionmixture blend of claim 1, wherein the polyol, natural sugar orartificial sugar is encapsulated with a sparingly soluble material. 12.The completion/stimulation/production fluid and injection mixture blendof claim 1, wherein the polyol, natural sugar or artificial sugar ispresent in the injection mixture in an amount of between 0.1% to 99% byweight of the completion/stimulation/production fluid and injectionmixture blend.
 13. The completion/stimulation/production fluid andinjection mixture of claim 1, wherein the injection mixture comprises acorrosion inhibitor, a biocide, a clay stabilizer, a friction reducer, ametal crosslinker that is borate, zirconium, aluminum, chromium,titanium, sand, or a combination thereof.
 14. Thecompletion/stimulation/production fluid and injection mixture of claim1, wherein the completion/stimulation/production fluid and injectionmixture does not include ethylenediaminetetraacetic acid (EDTA),propylenediaminetetraacetic acid (PDTA), nitrilotriacetic acid (NTA),N-(2-hydroxyethyl)ethylenediaminetriacetic acid (HEDTA),diethylenetriaminepentaacetic acid (DTPA), hydroxyethyliminodiaceticacid (HEIDA), cyclohexylenediaminetetraacetic acid (CDTA),diphenylaminosulfonic acid (DPAS),ethylenediiminodi(o-hydroxyphenylacetic) acid (EDDHA), glucoheptonicacid, gluconic acid, oxalic acid, malonic acid, succinic acid, glutaricacid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacicacid, phthalic acid, terephthalic acid, aconitic acid, carballylic acid,trimesic acid, isocitric acid, citric acid, acetic acid, erythorbicacid, formic acid, nitrilotriacetic acid (NTA), phosphonic acid, orsalts thereof.
 15. The completion/stimulation/production fluid andinjection mixture of claim 1, wherein thecompletion/stimulation/production fluid and injection mixture does notinclude a biocidal quaternary ammonium preservative.
 16. A compositioncomprising: an aqueous fluid; a polymer system; and a polyol, a naturalsugar, an artificial sugar, or a combination thereof.
 17. Thecomposition of claim 16, wherein the polymer system is polyacrylamideslickwater, polyacrylamide slickwater-crosslinked, guar gum, guar gumand crosslinker, guar derivative, guar derivative crosslinked, carboxymethyl cellulose (CMC), or CMC crosslinked.
 18. The composition of claim16, wherein the polymer system includes: a polymer comprising monomericunits, wherein the monomeric units comprise: component (A) representedby the formula:

wherein within component (A), R₁ is hydrogen, a C₁-C₆ alkyl, or aphenyl; R₂ is a C₁-C₂₂ alkylene, a carboxylic C₁-C₂₂ alkylene ester,benzyl, an alkyl benzyl containing C₁-C₁₆ carbon atoms, or a benzylamide; and X is hydrogen, lithium, sodium, potassium, ammonium or amixture thereof; or component (B) represented by the formula:

wherein within component (B), R₁ is hydrogen, a C₁-C₆ alkyl, or aphenyl; R₃ is a C₁-C₂₂ alkylene, a C₁-C₂₂ alkyl amide, a phenyl amide, abenzyl amide, a carboxylic C₁-C₂₂ alkylene ester, a phenyl, a benzyl, ora benzyl alkyl containing C₁-C₁₆ carbon atoms; and X is hydrogen,lithium, sodium, potassium, ammonium or a mixture thereof; or component(C) represented by the formula:

wherein within component (C), R₁ is hydrogen, a C₁-C₆ alkyl, or aphenyl; R₄ is a C₁-C₂₂ alkylene, a C₁-C₂₂ alkyl amide, a phenyl amide, abenzyl amide, a carboxylic C₁-C₂₂ alkylene ester, a phenyl, a benzyl, ora benzyl alkyl containing C₁-C₁₆ carbon atoms; and X is hydrogen,lithium, sodium, potassium, ammonium or a mixture thereof; or component(D) represented by the formula:

wherein within component (D), R₁ is hydrogen, a C₁-C₆ alkyl, or aphenyl; and R₅ is a C₁-C₂₂ alkylene, a C₁-C₂₂ alkyl amide, a phenylamide, a benzyl amide, a carboxylic C₁-C₂₂ alkylene ester, a benzyl, ora benzyl alkyl containing C₁-C₁₆ carbon atoms; or component (E)represented by the formula:

wherein within component (E), R₁ is hydrogen, a C₁-C₆ alkyl, or aphenyl; R₆ is hydrogen or an alkyl containing C₁-C₂₂ carbon atoms; andR₇ is hydrogen or an alkyl containing C₁-C₂₂ carbon atoms; or component(F) represented by the formula:

wherein within component (F), R₁ is hydrogen, a C₁-C₆ alkyl, or aphenyl; R₈ is a C₁-C₂₂ alkylene, a C₁-C₂₂ alkyl amide, a phenyl amide, abenzyl amide, a benzyl, or a benzyl alkyl containing C₁-C₁₆ carbonatoms; R₉ is hydrogen or an alkyl containing C₁-C₂₂ carbon atoms; andR₁₀ is hydrogen or an alkyl containing C₁-C₂₂ carbon atoms; or component(G) represented by the formula:

wherein within component (G), R₁ is hydrogen, a C₁-C₆ alkyl, or aphenyl; and R₁₁ is a carboxylic acid, a carboxylic salt, a sulfonicacid, a sulfonic salt, a phosphonic acid salt, an alcohol, an amine, ora nitrile; or component (H) represented by the formula:

wherein within component (H), R₁ is hydrogen, a C₁-C₆ alkyl, or aphenyl; R₁₂ is a C₁-C₂₂ alkylene, a C₁-C₂₂ alkyl amide, a phenyl amide,a phenyl, a phenyl alkylamino amide, or a phenyl alkyl containing C₁-C₁₆carbon atoms; R₁₃ is hydrogen, lithium, sodium, potassium, ammonium, ora mixture thereof; and R₁₄ is hydrogen, lithium, sodium, potassium,ammonium, or a mixture thereof; or component (I) represented by theformula:

wherein within component (I), R₉ is hydrogen or an alkyl containingC₁-C₂₂ carbon atoms; R₁₀ is hydrogen or an alkyl containing C₁-C₂₂carbon atoms; and Z is chlorine, bromine, iodine or a mixture thereof;or component (J) represented by the formula:

wherein within component (J), R₁ is hydrogen, a C₁-C₆ alkyl, or aphenyl; R₂ is a C₁-C₂₂ alkylene, a C₁-C₂₂ alkyl amide, a phenyl amide, aphenyl, a phenyl alkylamino amide, or a phenyl alkyl containing C₁-C₁₆carbon atoms; R₁₈ is hydrogen or an alkyl containing C₁-C₂₂ carbonatoms; R₁₆ is hydrogen or an alkyl containing C₁-C₂₂ carbon atoms; andR₁₇ is hydrogen or an alkyl containing C₁-C₂₂ carbon atoms; Y isnitrogen, phosphorus, sulfur or a mixture thereof; and Z is chlorine,bromine, iodine or a mixture thereof; or combinations thereof.
 19. Thecomposition of claim 16, wherein the polyol, natural sugar or artificialsugar is ethylene glycol, glycerol, erythritol, threitol, arabitol,xylitol, ribitol, sorbitol, galactitol, fucitol, inositols, volemitol,isomalt, maltitol, lactitol, maltotritol, maltoetraitol, polyglycitol,glucose, fructose, raffinose, a combination thereof, or a metal saltthereof.
 20. The composition of claim 16, wherein the polyol, naturalsugar or artificial sugar is Arabitol, Erythritol, Fucitol, Galactitol,Hydrogenated starch hydrolysates, Iditol, Isomalt, Lactitol, LycasinMaltitol, Mannitol, Mannosulfan, Ribitol, Sorbitol, Sorbitex, Threitol,Volemitol, Xylitol, combinations thereof, or a metal salt thereof. 21.The composition of claim 16, wherein the polyol, natural sugar orartificial sugar is Fructose, Galactose, Glucose, Xylose, Dioses,Trioses, Tetroses, Pentoses, Hexoses, Heptoses, Octoses, Nonoses,combinations thereof, or a metal salt thereof.
 22. The composition ofclaim 16, wherein the polyol, natural sugar or artificial sugar is adisaccharide or a metal salt thereof.
 23. The composition of claim 16,wherein the polyol, natural sugar or artificial sugar is Ascorbic acid,Glucuronic acid, Sulfoquinovose, Sialic acid, Glucosamine,Galactosamine, Lactic Acid, polylactic acid, combinations thereof, or ametal salt thereof.
 24. The composition of claim 16, wherein the polyol,natural sugar or artificial sugar is cyclitol or a metal salt thereof.25. The composition of claim 16, wherein the polyol, natural sugar orartificial sugar is tetrol.
 26. The composition of claim 16, wherein thepolyol, natural sugar or artificial sugar is encapsulated with asparingly soluble material.
 27. The composition of claim 16, wherein thecomposition comprises a corrosion inhibitor, a biocide, a claystabilizer, a friction reducer, a metal crosslinker that is borate,zirconium, aluminum, chromium, titanium, sand, or a combination thereof.28. The composition of claim 16, wherein the composition does notinclude ethylenediaminetetraacetic acid (EDTA),propylenediaminetetraacetic acid (PDTA), nitrilotriacetic acid (NTA),N-(2-hydroxyethyl)ethylenediaminetriacetic acid (HEDTA),diethylenetriaminepentaacetic acid (DTPA), hydroxyethyliminodiaceticacid (HEIDA), cyclohexylenediaminetetraacetic acid (CDTA),diphenylaminosulfonic acid (DPAS),ethylenediiminodi(o-hydroxyphenylacetic) acid (EDDHA), glucoheptonicacid, gluconic acid, oxalic acid, malonic acid, succinic acid, glutaricacid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacicacid, phthalic acid, terephthalic acid, aconitic acid, carballylic acid,trimesic acid, isocitric acid, citric acid, acetic acid, erythorbicacid, formic acid, nitrilotriacetic acid (NTA), phosphonic acid, orsalts thereof.
 29. The composition of claim 16, wherein the compositiondoes not include a biocidal quaternary ammonium preservative.